The-main



Patented Apr. 13, 1926.

UNITED STATES 1.580.1 9 PATENT. OFFICE.

ARTHUR ZITSOHER AN D ROBERT SOHMITT, OF OFFENBACH-OE-THE-MAIN, GERMANY,

ASSIGNORS TO OHEMISCHE FABRIK GRIESHEIM- ELEKTRON, OF FRANKFORT-ON- THE-MAIN GERMANY, A CORPORATION.

DI-AOYLAGETYL-DLAMINO COMPOUNDS OF THE ABOMATIG SERIES AND PROCESS OF MAKING SAME.

No Drawing.

wherein R and Rf represent the same or difierent aryl residues, Y any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms, X a connecting link of the character explained hereinafter.

. Under the definition givenfor Y we include aliphatic as well as aromatic radicles, un-

derthe term connectin link for Xatoms and atom complexes suc as O, S, CH GOJ'T, 'NH1 "'a N' 2 N- NH- CHr-O- 1i- O NH-"(iH -AF and the like, which in our present invention form a. connection between the two aryl residues, as indicated by the general formula given above. The vprocess of pounds consists in heating acylacetic acid making the com-- Application filed May 15,1923. Serial No. 639,214.

esters, such as acetoacetic acid ester or its homologues or analogues, with the corresponding diamins, such as e. g. thioanilin, dlaminodiphen lether, diaminoditolylmethan, diamino enzophenon, diaminodiphenylamm, aminobenzoylphenylenediamin, diaminoazobenzene, diammoazoxybenzene, diaminodiphenylurea, aminophenolethylene ether and others, preferably in a solvent or diluent. i

The new di-acylacetyl-diamino compounds may be used as primary products for the production of dyestuffs.

The following examples illustrate the invention, the parts being byweight, and all temperatures in centigrade degrees.

' Ewample 1.

' Into a. mixture, heated to 175-180, of 205 parts of acetoacetic acid ester and 200 parts of mtrobenzene 76 parts of 4.4'-diaminobenzophenon are poured while stirring. The mixture is held at 170-180, until the reaction is finished. The pulp of crystals,

formed after cooling down, is filtered, freed of nitrobenzene by means of ether and dried.- Thedi-acetoacetyl-4.4-diaminobenzophenon,

obtained in a yleld of 68 p. 01,01 the theoreticalyield, is crystallized from much waterin colorless lustrous needles, melting at 175-176 C. (not corrected) with a feeble decomposition. The formula of this product is mcoomcoJiaOc -ONmco.cmoocrt,

acetic acid ester',g-kept-'boiling, 'until the. splitting off of alcohol is finished, and the product of the reaction is worked up in the usual manner. 116 parts of di-acetoacetyl- 4.4'-diaminoazobenzene, that, is 76 c.-of the theoretical yield, are obtained. rystallized from dilute acetic acid it forms an orange-yellow crystalline powder, decompos- .ing at 233-234 (not corrected). The producti-obtainedin this example has ti" formula I cm.co.cm.oo.mz mmO-Nmooomcocm aryl residues, Z enact a group of connecting This product is one of a group corresponding to the general formula .l

where R and R meanthe same or dilferent links comprising N=N O l| I and Y any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms.

Instead of the acetoacetic acid ester its analogues such as e. g. benzoylacetic acid ester, can be used for the process, as diamins e. g. thioanilin, diaminodiphenylether, di-

aminodiphenylamin, diaminodiphenylurea, aminobenzoylphenylenediamin and others are available.

The following table gives the properties of some of the compounds obtainable according to the present process:

Dl-acylaoetyl-. Crystalized Melting point C.

compound. Aspect from. not corrected. Solubmty' Di-acetoacetyl -4.4'-diami- Fine, colorless little Acetic acid 138-139f under decom- Soluble in alcohol and glacial acetic no -3.3- dichlorodiplienylcrystals. position. acid, insoluble in ether.

methan. Dl-acetoacetyl-Lfldiamino- Colorless clin gin g Alcohol 143-144 under dccom- Soluble in alcohol and nitrobcnzene, 3.3'-ditolylmethan. needles. position. insoluble in carbontetrachloride. Di-acetoacetyl-4.4-diamino- Colorless ln s t r o u 5 Much water 175-176 under feeble Wall soluble in alcohol and glacial acetic benzophenon. needles. decomposition. gglld, a little soluble in ether and uene. Di-acetoacetyl-4.4'-dlami- Yellow needles Dilute acetic acid: 233-234 under decom- Soluble in glacial acetic acid, nitronoazobenzene. position. benzene and pyridine, a little soluble in ether and toluene. Dl-aoetoacetyl-4.4-dlamino- Brownish yellow crys- Dilute acetic acid. 219-220 under decom- Soluble in alcohol and glacial acetic azoxybenzene. talline powder. position. acid insoluble in ether. Di-acetoacctyl-4.4-diami- Clearly yellow pow- Alcohol. 215 under decompo- Soluble in alcohol and glacial acetic no-3.3-a zotoluene. der. sltlon. acid, insoluble in ether. I Di-ncetoacetyl-4.4'-diainino- Colorless lustrous leaf- Acetic acid Over 320 Soluble in lacial acetic acid and diphenlym'ea. lets. pyridine, scarcely soluble in acetone,

alcohol and xylene.

The formulas of several of the products specified above are as follows: The formula of di-acetoacetyl-i.4-diamino-3.3-dichlorodiphenylmethane is omooomoounOwn NH.CO.CH,.CO.CH;

Di acetoacetyl-4AJ-diaminoazoxybenzene has the formula CHa.C0.0Hg-CO.NH

Di acetoacetylixl'-diamino-diphenylurea has the formula cmooomoonnOma.oomONHooomoooHi 2. As new articles the di-acylacetyl-diaminocompounds of the general formula:

R and R meaning the same or different aryl residues, X one of a group of connecting links com rising -O, -s-- CH,, -oo H -NH.oo-,-i-I=N-,

and Y any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms.

3. As new articles the di-acylacetyl-diaminocompounds of the general formula:

R and R meaning the same or different aryl residues, Z one of a cup of connecting links, comprising --N" containing two N-atoms, and Y any radicle of the hy rocarbon series containing at least one and not more than six carbon atoms.

4. As a new article di-acetoacetyl-diaminoazobenzene of the formula:

In testimony, that we claim the foregoing as our invention, We have signed our names, this 28th day of April 1923.

ARTHUR ZITSCHER. [1,. 8.] ROBERT SGHMITT. [ns] 

